Method for separating nickel from cobalt

Claim 2

A process for the separation of individual metal compounds from an aqueous solution of metal halides comprising as the primary solute, a compound of manganese, and as secondary solutes, compounds of cobalt and nickel, the process comprising (1) adjusting the pH of the solution to a value within the desired range of from about 3 to about 6; (2) contacting the aqueous solution with an organic solution of a liquid ion exchange agent, the agent being selected from the group consisting of Alpha -hydroxy oximes and hydrocarbon-substituted-8-hydroxyquinolines, to extract nickel and cobalt and maintaining the pH within the desired range until the aqueous solution is substantially depleted in nickel and cobalt, thus forming an organic extract liquid solution containing dissolved nickel and cobalt values and an aqueous raffinate containing manganese compound and substantially depleted in nickel and cobalt; (3) selectively stripping the nickel value from the organic extract with an acidic aqueous solution of a mineral acid, which does not strip cobalt, to form an organic phase substantially depleted of nickel and an aqueous phase containing a nickel salt; and (4) stripping the cobalt value from the organic phase using an aqueous acid solution containing a hydrogen ion and a halide ion concentration of at least 6N each to form an organic phase substantially depleted in nickel and cobalt values and an acidic aqueous phase containing a cobalt halide.

Claim 3

A process in accordance with claim 1 comprising, in addition, (5) contacting the acidic aqueous phase with an organic amine solution to extract the cobalt value to form an organic amine complex containing the cobalt value, and (6) stripping the cobalt value form the amine with an aqueous liquid form an aqueous solution of the cobalt halide.

Claim 4

A process in accordance with claim 1, wherein the liquid ion exchange agent is a hydrocarbon-substituted 8-hydroxyquinoline substituted in the 7-position with a beta-alkenyl group or an alkylbenzyl group.

Claim 5

A process in accordance with claim 1, wherein the liquid ion exchange agent is an Alpha -hydroxyoxime wherein in the formula:

Claim 6

A process in accordance with claim 1, wherein the nickel is stripped from the extract with an aqueous solution having a concentration of hydrogen ion of from about 0.1 to about 3 Normal.

Claim 7

A PROCESS FOR OBTAINING, INDIVIDUALLY, THE NICKEL AND COBALT VALUES FROM OCEAN FLOOR NODULE ORE, THE ORE COMPRISING, AS MAJOR COMPONENTS THE OXIDES OF MANGANESE AND OF IRON. AND AS SECONDARY COMPONENTS, COMPOUNDS OF COPPER, COBALT AND NICKEL, THE PROCCESS COMPRISING THE STEPS OF (A) REACTING THE OCEAN FLOOR NODULE ORE WITH A HALIDE-FORMING AGENT UNDER REDUCING CONDITIONS TO FORM A MIXTURE COMPRISING THE CORRESPONDING WATERSOLUBLE METAL HALIDE SALTS OF DIVALENT MANGANESE, TRIVALENT IRON, COPPER, NICKEL AND COBALT: (C) SEPARATING THE IRON FROM THE REMAINING SALTS AND FORMING AN AQUEOUS SOLUTION OF THE WATERSOLUBLE METAL HALIDE SALTS: (C) ADJUSTING THE PH OF THE AQUEOUS SOLUTION TO A VALUE OF NOT GREATER THAN ABOUT 2.5: (D) CONTACTING THE AQUEOUS SOLUTION WITH A LIQUID ION EXCHANGE EXTRACTING MEDIUM IMMISCIBLE WITH WATER, THE MEDIUM COMPRISING AN EXTRACTING AGENT SELECTED FROM THE GROUP CONSISTING OF SUBSTITUTED 8-HYDROXY-QUINOLINES, ALPHAHYDROXY OXIMES, AND NAPTHENIC ACIDS TO EXTRACT COPPER SELECTIVELY FROM THE SOLUTION, UNTIL THE AQUEOUS SOLUTION IS SUBSTANTIALY DEPLETED IN COPPER, THUS FORMING AN ORGANIC EXTRACT CONTAINING THE COPPER VALUE AND A FIRST AQUEOUS RAFFINATE SOLUTON SUBSTANTIALLY DEPLETED IN COPPER: (C) ADJUSTING THE PH OF THE FIRST AQUEOUS RAFFINATE SOKUTION TO A VALUE WITHIN THE DESIRED RANGE OF FROM ABOUT 3 TO 6: (F) CONTACTING THE FIRST RAFFINATE WITH AN ORGANIC SOLUTION OF A LIQUID ION EXCHANGE AGENT, THE AGENT BEING SELECTED FROM THE GROUP CONSISTING OF A-HYDROXY OXIME AND HYDROCARBON-SUBSTITUTED-8-HYDROXYQUINOLINES, TO EXTRACT NICKEL AND COBALT, AND MAINTAINING THE PH WITHIN THE DESIRED RANGE UNTIL TH AQUEOUS SOLUTION IS SUBSTANTIALLY DEPLETED IN NICKEL AND CCOBALT, THUS FORMING A ORGANIC EXTRACT LIQUID SOLUTION CONTAINING DISSOLVED NICKEL AND COBALT VALUE AND AN AQUEOUS RAFFINATE CONTAINING MANGANESE COMPOUND AND SUBSTANTIALY DEPLETED IN NICKEL AND COBALT: (G) SELECTIVELY STRIOOING THE NICKEL VALUE FROM THE ORGANIC EXTRACTS WITH AN ACIDIC AQUEOUS SOLUTION OF A MINERAL ACID, WHICH DOES NOT STRIP COBALT, TO FORM AN ORGANIC PHASE SUBSTANTIALLY DEPLETED OF NICKEL AND AN AQUEOUS PHASE CONTAINING A NICKEL SALT, AND (H) STRIPPING THE COBALT VALUE FROM THE ORGANIC PHASE USING AN AQUEOUS ACID SOLUTION CONTAINING A HYDROGEN ION AND A HALIDE ION CONCENTRAION OF AT LEAST 6N EACH TO FORM AN ORGANIC PHASE SUBSTANTIALLY DEPLETED IN NICKEL AND COLBALT VALUES AND AN ACIDIC AQUEOUS PHASE CONTAINING A COBALT HALIDE

Claim 8

A PROCESS FOR OBTAINING, INDIVIDUALLY, THE NICKEL AND COBALT VALUES FROM OCEAN FLOOR NODULE ORE, THE ORE COMPRISING, AS MAJOR COMPONENTS THE OXIDES OF MANGANESE AND OF IRON. AND AS SECONDARY COMPONENTS, COMPOUNDS OF COPPER, COBALT AND NICKEL, THE PROCCESS COMPRISING THE STEPS OF (A) REACTING THE OCEAN FLOOR NODULE ORE WITH A HALIDE-FORMING AGENT UNDER REDUCING CONDITIONS TO FORM A MIXTURE COMPRISING THE CORRESPONDING WATERSOLUBLE METAL HALIDE SALTS OF DIVALENT MANGANESE, TRIVALENT IRON, COPPER, NICKEL AND COBALT: (C) SEPARATING THE IRON FROM THE REMAINING SALTS AND FORMING AN AQUEOUS SOLUTION OF THE WATERSOLUBLE METAL HALIDE SALTS: (C) ADJUSTING THE PH OF THE AQUEOUS SOLUTION TO A VALUE OF NOT GREATER THAN ABOUT 2.5: (D) CONTACTING THE AQUEOUS SOLUTION WITH A LIQUID ION EXCHANGE EXTRACTING MEDIUM IMMISCIBLE WITH WATER, THE MEDIUM COMPRISING AN EXTRACTING AGENT SELECTED FROM THE GROUP CONSISTING OF SUBSTITUTED 8-HYDROXY-QUINOLINES, ALPHAHYDROXY OXIMES, AND NAPTHENIC ACIDS TO EXTRACT COPPER SELECTIVELY FROM THE SOLUTION, UNTIL THE AQUEOUS SOLUTION IS SUBSTANTIALY DEPLETED IN COPPER, THUS FORMING AN ORGANIC EXTRACT CONTAINING THE COPPER VALUE AND A FIRST AQUEOUS RAFFINATE SOLUTON SUBSTANTIALLY DEPLETED IN COPPER: (C) ADJUSTING THE PH OF THE FIRST AQUEOUS RAFFINATE SOKUTION TO A VALUE WITHIN THE DESIRED RANGE OF FROM ABOUT 3 TO 6: (F) CONTACTING THE FIRST RAFFINATE WITH AN ORGANIC SOLUTION OF A LIQUID ION EXCHANGE AGENT, THE AGENT BEING SELECTED FROM THE GROUP CONSISTING OF A-HYDROXY OXIME AND HYDROCARBON-SUBSTITUTED-8-HYDROXYQUINOLINES, TO EXTRACT NICKEL AND COBALT, AND MAINTAINING THE PH WITHIN THE DESIRED RANGE UNTIL TH AQUEOUS SOLUTION IS SUBSTANTIALLY DEPLETED IN NICKEL AND CCOBALT, THUS FORMING A ORGANIC EXTRACT LIQUID SOLUTION CONTAINING DISSOLVED NICKEL AND COBALT VALUE AND AN AQUEOUS RAFFINATE CONTAINING MANGANESE COMPOUND AND SUBSTANTIALY DEPLETED IN NICKEL AND COBALT: (G) SELECTIVELY STRIOOING THE NICKEL VALUE FROM THE ORGANIC EXTRACTS WITH AN ACIDIC AQUEOUS SOLUTION OF A MINERAL ACID, WHICH DOES NOT STRIP COBALT, TO FORM AN ORGANIC PHASE SUBSTANTIALLY DEPLETED OF NICKEL AND AN AQUEOUS PHASE CONTAINING A NICKEL SALT, AND (H) STRIPPING THE COBALT VALUE FROM THE ORGANIC PHASE USING AN AQUEOUS ACID SOLUTION CONTAINING A HYDROGEN ION AND A HALIDE ION CONCENTRAION OF AT LEAST 6N EACH TO FORM AN ORGANIC PHASE SUBSTANTIALLY DEPLETED IN NICKEL AND COLBALT VALUES AND AN ACIDIC AQUEOUS PHASE CONTAINING A COBALT HALIDE

Claim 9

A process in accordance with claim 6, wherein the nickel is stripped from the extract with an aqueous solution having a concentration of hydrogen ion of from about 0.1 to about 3 Normal.

Claim 10

A process for the separation of nickel value from cobalt value from an aqueous solution of metal halides comprising as the primary solute, a compound of manganese, and as the secondary solutes, compounds of cobalt and nickel, by extraction from an aqueous solution followed by selective stripping, the process comprising: (1) contacting the aqueous solution with an organic solution of a liquid ion exchange agent, the agent being selected from the group consisting of alphahydroxy-oximes and hydrocarbon-substituted-8-hydroxyquinolines, to extract both nickel and cobalt from the aqueous solution while maintaining the pH within a desired range of from about 3 to about 6 until the aqueous solution is substantially depleted in nickel and cobalt, thus forming a liquid organic extract solution containing dissolved nickel and cobalt values and an aqueous raffinate containing manganese compound and substantially depleted in nickel and cobalt; and (2) selectively stripping the nickel value from the organic extract solution with an acidic aqueous solution of mineral acid, which does not strip cobalt, to form an organic phase containing cobalt and substantially depleted of nickel and an aqueous phase containing a nickel salt, and substantially free from cobalt.

Claim 11

A process for the separation of nickel value from cobalt value from an aqueous solution of metal halides comprising as the primary solute, a compound of manganese, and as the secondary solutes, compounds of cobalt and nickel, by extraction from an aqueous solution followed by selective stripping, the process comprising: (1) contacting the aqueous solution with an organic solution of a liquid ion exchange agent, the agent being selected from the group consisting of alphahydroxy-oximes and hydrocarbon-substituted-8-hydroxyquinolines, to extract both nickel and cobalt from the aqueous solution while maintaining the pH within a desired range of from about 3 to about 6 until the aqueous solution is substantially depleted in nickel and cobalt, thus forming a liquid organic extract solution containing dissolved nickel and cobalt values and an aqueous raffinate containing manganese compound and substantially depleted in nickel and cobalt; and (2) selectively stripping the nickel value from the organic extract solution with an acidic aqueous solution of mineral acid, which does not strip cobalt, to form an organic phase containing cobalt and substantially depleted of nickel and an aqueous phase containing a nickel salt, and substantially free from cobalt.

Claim 12

A process in accordance with claim 8, wherein the nickel is stripped from the extract with an aqueous solution having a concentration of hydrogen ion of from about 0.1 to about 3 Normal.

Claim 13

A process in accordance with claim 9, wherein the compounds of cobalt and nickel are chlorides.